TW201544562A - Adhesive composition, laminate, and stripping method - Google Patents

Abstract

There is provided an adhesive composition which is an adhesive composition for temporarily attaching a substrate to a support plate which supports the substrate, and includes a thermoplastic resin and a release agent.

Description

Substance composition, laminate and peeling method

The present invention relates to an adhesive composition, a laminate, and a peeling method.

The present application claims priority based on Japanese Patent Application No. 2014-088539 and Japanese Patent Application No. 2015-039457, filed on Jan. 22, 2014, and on February 27, 2015.

With the high performance of mobile phones, digital AV devices, and IC cards, there is a demand for miniaturization and thinning of semiconductor wafers (hereinafter referred to as wafers) to be mounted. Therefore, there is an increasing demand for high integration of the wafers in the package. For example, in an integrated circuit in which a plurality of wafers such as a CSP (chip size package) or an MCP (multi-chip package) are packaged, thinning is required. In order to achieve high integration of the wafer in the package, the thickness of the wafer needs to be reduced to a range of 25 to 150 μm.

However, a semiconductor wafer (hereinafter referred to as a wafer) which is a substrate of a wafer is thinned by polishing, and as a result, the strength thereof is weakened, and the wafer is liable to be cracked or warped. In addition, because the thickness is thin, it is difficult to automatically transport the strength. Attenuated wafers must be shipped by hand, making their handling more cumbersome.

Therefore, it has been developed to maintain the strength of the wafer and prevent the occurrence of cracks by adhering a flat plate made of glass, hard plastic or the like to the wafer to be polished via a subsequent layer of the so-called "support sheet". A warped wafer processing system for wafers. Since the wafer processing system (WHS) can maintain the strength of the wafer, the transportation of the thinned semiconductor wafer can be automated.

A method of manufacturing a semiconductor wafer in which a semiconductor wafer is processed by a semiconductor wafer bonding support and a support is separated, and the method described in Patent Document 1 is known. In the method described in Patent Document 1, the light-transmitting support and the semiconductor wafer are bonded to each other via a photothermal conversion layer and a subsequent layer provided on the support side, and then the semiconductor wafer is processed. The support side is irradiated with radioactivity to decompose the photothermal conversion layer, and the semiconductor wafer is separated from the support.

Prior technical literature [Patent Document]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-64040 (published on Feb. 26, 2004)

However, in the technique described in Patent Document 1, in order to prevent the substrate and the support from being peeled off during the treatment, a high adhesion is used. The agent composition forms a laminate. Therefore, before the formation of the laminate, a step of forming a separation layer which absorbs light and deteriorates on the support is required. Further, after the substrate is subjected to a desired treatment, in order to peel the support from the substrate, a step of illuminating the separation layer formed on the laminate to be deteriorated is required.

Therefore, there is a need for a novel adhesive composition which can form a laminate in which the support layer is peeled off from the substrate without forming a separation layer.

The present invention has been made in view of the above problems, and an object thereof is to provide a novel adhesive composition which can form a laminate in which a support layer is easily peeled off from a substrate without forming a separation layer.

In order to solve the above problems, the adhesive composition of the present invention is an adhesive composition for temporarily bonding a substrate and a support for supporting the substrate, and is characterized by comprising a thermoplastic resin and a release agent.

According to the present invention, it is possible to provide a novel adhesive composition which can form a laminate in which a support layer can be easily peeled off from a substrate without forming a separation layer.

1‧‧‧Substrate

2‧‧‧Support board (support)

3‧‧‧Next layer

10‧‧‧Layer

11‧‧‧Layer

2a‧‧‧Support board (support)

21‧‧‧Laser illumination device

Fig. 1 is a schematic perspective view for explaining a laminate according to an embodiment of the present invention and a peeling method including a pretreatment step according to an embodiment of the present invention.

Figure 2 is a view showing a laminate according to an embodiment of the present invention, and A schematic perspective view of a peeling method including an illuminating step according to an embodiment of the present invention.

<Binder composition>

Hereinafter, the adhesive composition according to an embodiment of the present invention will be described in detail with reference to Fig. 1 .

The adhesive composition of one embodiment is used for temporarily bonding the substrate 1 and the adhesive composition of the support sheet (support) 2 of the support substrate 1, which comprises a thermoplastic resin and a release agent (Fig. 1) (a)).

According to the above configuration, the adhesion of the adhesive layer 3 formed by the adhesive composition can be appropriately adjusted. Therefore, when the substrate 1 is subjected to a desired treatment, the substrate 1 and the support plate 2 can be appropriately attached via the adhesive layer 3. Moreover, after performing the desired treatment on the substrate 1, the support plate 2 can be easily peeled off from the substrate 1. Therefore, it is not necessary to form a separation layer on the support plate 2 before bonding the substrate 1 and the support plate 2. In other words, when the adhesive composition of one embodiment is used, it is possible to form a laminate in which the support layer 2 is peeled off from the substrate 1 without forming a separation layer which is deteriorated by absorption of light.

[thermoplastic resin]

The thermoplastic resin is a resin contained in the adhesive composition, and the substrate 1 and the support sheet 2 are bonded by the adhesion of the thermoplastic resin. Below, this is the real The composition of the thermoplastic resin contained in the adhesive composition of the embodiment will be described.

As the thermoplastic resin, for example, a thermoplastic resin which is used in various fields such as acrylic, phenolic, naphthoquinone, hydrocarbon, polyimide, or elastomer in various fields can be used.

The thermoplastic resin may, for example, be an elastomer resin, a hydrocarbon resin, an acrylic-styrene resin, a maleic imine resin, or the like.

The glass transition temperature (Tg) of the subsequent composition varies depending on the kind or molecular weight of the thermoplastic resin, and the kind or amount of the plasticizer blended in the adhesive composition. The type or molecular weight of the thermoplastic resin contained in the composition of the second embodiment can be appropriately selected depending on the type of the substrate and the support, but the Tg of the thermoplastic resin used in the adhesive composition is preferably in the range of -60 ° C or more and 200 ° C or less. More preferably, it is in the range of -25 ° C or more and 150 ° C or less. The Tg of the thermoplastic resin used in the composition of the second embodiment is in the range of -60 ° C or more and 200 ° C or less, and does not require excessive energy during cooling, and the adhesion of the adhesive layer 3 can be appropriately lowered. Further, the Tg of the subsequent layer 3 can also be adjusted by appropriately blending a plasticizer or a resin having a low degree of polymerization.

(elastomer)

The thermoplastic resin contained in the adhesive composition of one embodiment is preferably an elastomer.

Heat resistance can be obtained by using an elastomer using a thermoplastic resin An adhesive composition that is high and resistant to photoresist solvents.

The elastomer preferably contains a styrene unit as a constituent unit of the main chain, and the "styrene unit" may have a substituent. The substituent may, for example, be an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an ethoxy group or a carboxyl group. Further, the content of the styrene unit is more preferably in the range of 14% by weight or more and 50% by weight or less. Further, the weight average molecular weight of the elastomer is preferably in the range of 10,000 or more and 200,000 or less.

When the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, it is easily dissolved in a hydrocarbon solvent to be described later. The subsequent layers are removed more easily and quickly. Further, by the content of the styrene unit and the weight average molecular weight within the above range, the photoresist which is exposed when the wafer is subjected to the photoresist lithography step (for example, propylene glycol monomethyl ether acetate (PGMEA)) can be exhibited. Excellent resistance to propylene glycol monomethyl ether (PGME), acid (hydrofluoric acid, etc.), alkali (tetramethylammonium hydroxide (TMAH), etc.).

Further, in the elastomer, a (meth) acrylate described later may be further blended.

Further, the content of the styrene unit is preferably 17% by weight or more, and more preferably 40% by weight or less.

The weight average molecular weight is preferably in the range of 20,000 or more; more preferably, it is in the range of 150,000 or less.

As an elastomer, as long as the content of styrene units is 14 In the range of % by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, various elastomers can be used. For example, polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene embedded Segmented copolymer (SBS), styrene-butadiene-butene-styrene block copolymer (SBBS), and the like, hydride, styrene-ethylene-butylene-styrene block copolymer ( SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymerization (SEEPS) and styrene block are a reaction-crosslinking type styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (manufactured by KURARAY Co., Ltd.), Septon V9475 (manufactured by KURARAY Co., Ltd.)), The styrene block is a reaction-crosslinked type styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by KURARAY Co., Ltd.) having a reactive polystyrene-based hard block), and polystyrene - Poly(ethylene-ethylene/propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modification) and the like. The content of the styrene unit of the elastomer and the weight average molecular weight may be within the above range.

Among the above elastomers, a hydrogenated elastomer is more preferred. This is because the hydrogenated elastomer has high heat stability and is less susceptible to deterioration such as decomposition or polymerization. Further, the hydrogenated elastomer is also preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a resist solvent.

In addition, the elastomer is more preferably embedded at both ends via styrene Segment polymer. The reason for this is that the elastomer exhibits higher heat resistance by fitting styrene having high thermal stability at both ends.

The elastomer contained in the adhesive composition of one embodiment is more preferably a hydrogenated styrene elastomer among the above elastomers.

The hydrogenated styrene elastomer system refers to a hydride of a block copolymer of styrene and a conjugated diene. That is, the hydrogenated styrene elastomeric system has the same advantages as the hydrogenated elastomer and the advantages of the block polymer.

Therefore, by using the hydrogenated styrene elastomer as the thermoplastic resin, the stability of the adhesive layer 3 formed by the adhesive composition can be further improved, and the adhesive layer 3 can be prevented from being deteriorated by decomposition or polymerization. Moreover, the heat resistance of the adhesive layer 3 can be further improved. Further, the hydrogenated styrene elastomer is preferably used as a thermoplastic resin from the viewpoints of solubility in a hydrocarbon solvent and resistance to a photoresist solvent.

For example, "Septon (trade name)" manufactured by KURARAY Co., Ltd. and "Hybrar (trade name)" manufactured by KURARAY Co., Ltd., as a commercially available product which can be used as an adhesive for the adhesive layer 3, may be mentioned. "Taftec (trade name)" manufactured by Asahi Kasei Co., Ltd., "DYNARON (trade name)" manufactured by JSR Co., Ltd., etc.

The content of the elastomer contained in the adhesive constituting the adhesive layer 3 is, for example, 100 parts by weight or more, preferably 50 parts by weight or more and 99 parts by weight or less, more preferably 60 parts by weight, based on the total amount of the adhesive composition. In the range of the weight part or more and 99 parts by weight or less, it is preferably in the range of 70 parts by weight or more and 95 parts by weight or less. By making it here In the same range, heat resistance can be maintained, and the wafer and the support can be appropriately bonded.

Further, in terms of the elastomer, a plurality of types may be mixed. That is, the adhesive constituting the adhesive layer 3 may also contain a plurality of elastomers. At least one of the plurality of elastomers may contain a styrene unit as a constituent unit of the main chain. Moreover, it is within the scope of the present invention if the content of the styrene unit of at least one of the plurality of elastomers is in the range of 14% by weight or more and 50% by weight or less, or the weight average molecular weight is in the range of 10,000 or more and 200,000 or less. . Further, when a plurality of elastomers are contained in the adhesive constituting the adhesive layer 3, the content of the styrene unit can be adjusted to the above range as a result of mixing. For example, Septon 4033 of Septon (trade name) manufactured by KURARAY Co., Ltd., and Septon 2063 of Septon (trade name) having a styrene unit content of 30% by weight in a weight ratio of 1% by weight. When 1 is mixed, the styrene content of the entire elastomer contained in the adhesive is 21 to 22% by weight, and is 14% by weight or more. Further, for example, when 10% by weight of the styrene unit and 60% by weight are mixed at a weight ratio of 1 to 1, the ratio is 35% by weight, which is within the above range. The invention may also be in this form. Further, it is preferable that the plurality of elastomers contained in the adhesive constituting the adhesive layer 3 contain styrene units in the above range and have a weight average molecular weight within the above range.

(hydrocarbon resin)

The thermoplastic resin contained in the adhesive composition of one embodiment is more preferably Hydrocarbon resin.

When a hydrocarbon resin is used as the thermoplastic resin, the adhesive layer 3 having higher heat resistance can be formed.

The hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerizing a monomer composition. The hydrocarbon resin may, for example, be a cycloolefin polymer (hereinafter referred to as "resin (A)"), and at least one resin selected from the group consisting of terpene resins, rosin resins, and petroleum resins ( Hereinafter, it is called "resin (B)"), etc., but it is not limited to this.

The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin monomer. Specifically, a ring-opening (co)polymer containing a monomer component of a cycloolefin type monomer and a resin obtained by addition (co)polymerization of a monomer component containing a cycloolefin type monomer are mentioned.

Examples of the cycloolefin-based monomer contained in the monomer component constituting the resin (A) include a bicyclic compound such as norbornene and norbornadiene, dicyclopentadiene, and hydroxydicyclopentadiene. a tricyclic substance such as a tricyclic substance or a tetracyclododecene, a pentacyclic substance such as a cyclopentadiene trimer, a heptacyclic substance such as tetracyclopentadiene or an alkyl group of such a polycyclic substance. (methyl, ethyl, propyl, butyl, etc.) substituted, alkenyl (vinyl or the like) substituted, alkylene (ethylene, etc.) substituted, aryl (phenyl, tolyl, naphthyl) Etc.) Substitutes, etc. Among these, a norbornene-based monomer selected from the group consisting of norbornene, tetracyclododecene, or an alkyl substituent thereof is preferred.

The monomer component constituting the resin (A) may further contain another monomer copolymerizable with the above cycloolefin-based monomer, and for example, preferably contains an olefin monomer. Examples of the olefin monomer include ethylene, propylene, 1-butene, and the like. Butene, 1-hexene, α-olefin, and the like. The olefin monomer may be linear or branched.

Further, the monomer component constituting the resin (A) preferably contains a cycloolefin monomer from the viewpoint of high heat resistance (low thermal decomposition and thermogravimetric reduction). The ratio of the cycloolefin monomer to the entire monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more. Further, the ratio of the cycloolefin monomer to the entire monomer component constituting the resin (A) is not particularly limited, and is preferably 80 mol% or less, more preferably 70 mol, from the viewpoint of solubility and stability over time in the solution. Less than the ear.

Further, the monomer component constituting the resin (A) may contain a linear or branched olefin monomer. The ratio of the olefin monomer to the entire monomer component constituting the resin (A) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, more preferably from 30 to 85 mol%, based on solubility and flexibility. 80% by mole.

In addition, in the case of suppressing the generation of a gas at a high temperature, the resin (A) preferably has a polarity such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an olefin monomer. Base resin.

The polymerization method, the polymerization conditions, and the like when the monomer component is polymerized are not particularly limited, and may be appropriately set according to a usual method.

As a commercial product which can be used as the resin (A), for example, "TOPAS" manufactured by Polyplastics Co., Ltd., "APEL" manufactured by Mitsui Chemicals Co., Ltd., "ZEONOR" and "ZEONEX" manufactured by Japan ZEON Co., Ltd., JSR Co., Ltd. "ARTON" and so on.

The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C or higher, and particularly preferably 70 ° C or higher. When the glass transition temperature of the resin (A) is 60 ° C or more, the softening of the adhesive layer 3 can be further suppressed when the laminate is exposed to a high temperature environment.

The resin (B) is at least one selected from the group consisting of a terpene resin, a rosin resin, and a petroleum resin. Specifically, examples of the terpene-based resin include a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, and a hydrogenated terpene phenol resin. Examples of the rosin-based resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of the petroleum resin include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and benzofuran-indene petroleum resins. Among these, a hydrogenated terpene resin and a hydrogenated petroleum resin are more preferable.

The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160 °C. When the softening point of the resin (B) is 80 ° C or more, the occurrence of softening can be suppressed when the laminate is exposed to a high temperature environment without causing defective defects. On the other hand, when the softening point of the resin (B) is 160 ° C or less, the peeling speed at the time of peeling the laminate is good.

The weight average molecular weight of the resin (B) is not particularly limited, and is preferably from 300 to 3,000. When the weight average molecular weight of the resin (B) is 300 or more, heat resistance is sufficient, and the amount of exhaust gas is reduced in a high temperature environment. On the other hand, if the weight average molecular weight of the resin (B) is 3,000 or less, peeling The peeling speed at the time of leaving the laminate was good. Further, the weight average molecular weight of the resin (B) of the present embodiment means a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

Further, as the resin, a resin (A) and a resin (B) may be used in combination. By mixing, the heat resistance and the peeling speed are good. For example, in the mixing ratio of the resin (A) and the resin (B), (A): (B) = 80: 20 to 55: 45 (mass ratio) due to the peeling speed, heat resistance in a high temperature environment, and softness Excellent and better.

(acrylic-styrene resin)

As the thermoplastic resin, an acrylic-styrene resin can also be used. The acrylic-styrene-based resin may, for example, be a resin obtained by copolymerizing a derivative of styrene or styrene or a monomer such as (meth)acrylate.

The (meth) acrylate may, for example, be an alkyl (meth)acrylate composed of a chain structure, a (meth) acrylate having an aliphatic ring, or a (meth) acrylate having an aromatic ring. Examples of the (meth)acrylic acid alkyl ester having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms, and an acrylic alkyl group having an alkyl group having 1 to 14 carbon atoms. Ester and the like. Examples of the acrylic long-chain alkyl esters include n-pentadecyl groups, n-hexadecyl groups, n-heptadecyl groups, n-octadecyl groups, n-nonadecyl groups, and n-icosyl groups. An alkyl ester of acrylic acid or methacrylic acid. Further, the alkyl group may also be branched.

An acrylic alkyl group having an alkyl group having 1 to 14 carbon atoms The ester may, for example, be a known acrylic alkyl ester used in a conventional acrylic adhesive. For example, an alkyl group is methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isodecyl, isodecyl, dodecyl, lauryl, tridecyl An alkyl ester of acrylic acid or methacrylic acid.

Examples of the (meth) acrylate having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, and (methyl). Acrylic acid norbornete ester, isobornyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetracyclododecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc., more preferably A Isobornyl acrylate, dicyclopentanyl (meth) acrylate.

The (meth) acrylate having an aromatic ring is not particularly limited, and examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, and a fluorenyl group. Phenoxymethyl, phenoxyethyl and the like. Further, the aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred.

(Malay ylide resin)

A maleic imine type resin can also be used as the thermoplastic resin. Examples of the maleic imine resin include N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, and N as monomers. -isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-butyl butyl maleimide, N-tertiary butyl Malayia Amine, N-n-pentylmaleimide, N-n-hexylmaleimide, N-n-heptylmaleimide, N-n-octylmaleimide, N-lauryl horse Alkyl-maleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N, such as imine, N-octadecylmaleimide, etc. - Maleic anthracene having an aliphatic hydrocarbon group such as cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide or the like Imine, N-phenylmaleimide, N-m-methylphenylmaleimide, N-o-methylphenylmaleimide, N-p-methylphenylmalaine A resin obtained by polymerization of an aromatic maleic imine or the like having an aryl group such as an amine.

For example, a cyclic olefin copolymer of a repeating unit represented by the following chemical formula (1) and a copolymer of a repeating unit represented by the following chemical formula (2) can be used as a resin for the subsequent component.

In the chemical formula (2), n is an integer of 0 or 1 to 3.

As such a cyclic olefin copolymer, APL 8008T, APL 8009T, and APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

[release agent]

The adhesive composition of one embodiment comprises a release agent. The adhesion of the adhesive layer 3 to the substrate 1 and the support sheet 2 can be adjusted by blending the release agent with the release agent. Thereby, it is possible to obtain an adhesive composition which can easily peel the laminate 10 of the support sheet 2 from the substrate 1 after performing the desired treatment on the substrate 1.

The mold release agent may, for example, be Silicone. More specifically, the fluorene ketone may, for example, be eucalyptus oil, and specific examples thereof include a pure eucalyptus oil, a modified eucalyptus oil, and a cured product of the modified eucalyptus oil.

(pure oyster sauce)

Examples of the pure eucalyptus oil include dimethyl hydrazine oil, methyl phenyl hydrazine oil, and methylhydroquinone oil. As an example of such a pure eucalyptus oil, a product manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned, and examples thereof include dimethyl groups such as KF96-10, KF96-100, KF96-1000, KF96H-10000, KF96H-12500, and KF96H-10000. Emu oil; methyl phenyl hydrazine oil such as KF50-100, KF54 and KF56; methyl hydroquinone oil such as KF99 and KF9901.

(modified oyster sauce)

The modified eucalyptus oil is an fluorenone modified by introducing a functional group to at least a part of the terminal and side chains of dimethyl fluorenone. That is, the modified eucalyptus oil is a modified ketone which is a two-terminal type, a single-end type, a side chain type, and a side chain type.

The modified eucalyptus oil may, for example, be a compound having a polydimethylsiloxane skeleton represented by the following chemical formulas (3) to (6):

In the chemical formulae (3) and (4), m is an integer of 1 or more, more preferably an integer of 10 or more and 1,000 or less, and still more preferably an integer of 20 or more and 500 or less. Further, in the chemical formulae (5) and (6), p is an integer of 1 or more, more preferably an integer of 10 or more and 1,000 or less, and still more preferably an integer of 20 or more and 500 or less. q is an integer of 1 or more, more preferably an integer of 10 or more and 1000 or less, and more preferably an integer of 20 or more and 500 or less. Further, in the chemical formulae (3) to (6), R is a methyl group, an epoxy group, an amine group, an acryl group, a methacryl group, a carboxyl group, a phenol group, a decyl group, an alkyl group or an aralkyl group. Functional groups of diols, sterol groups, polyethers, carboxylic anhydrides, higher fatty acid esters, higher fatty acid decylamines, and methylstyryl groups. Further, when a sterol group is introduced, R may be a hydroxyl group.

Further, when R is a functional group into which a polyether can be introduced, R can be represented by the following chemical formula (7): [Chemical 3]-R'-(C ₂ H ₄ O) _a -(C ₃ H ₆ O) _b -R "...(7)

In the chemical formula (7), R' is an organic group such as an alkylene group, and R' is a hydrogen atom or a linear or branched alkyl group which may be substituted by an aryl group or a cycloalkyl group. In a and b, a is an integer of 0 or more and 30 or less, and b is an integer of 0 or more and 30 or less, and satisfies the condition of 60≧a+b≧1.

In addition, the functional group equivalent of the modified eucalyptus oil is not particularly limited, and is preferably, for example, 1 g/mol or more and 100000 g/mol or less, more preferably 10 g/mol or more and 5,000 g/mol or less.

Further, when the modified fluorenone is modified with a functional group capable of introducing a hydroxyl group such as a methanol group, a phenol group or a polyether, the valence of the hydroxy group of the modified fluorenone is preferably 20 mgKOH/g or more and 500 mgKOH/g or less.

For example, X-22-4039, X-22-4015, KF6000, KF6001, KF6002, KF6003, and X-22 may be mentioned as an example of the oil of the fluorenone. -170DX and other methanol modified eucalyptus oil; X-22-163A, X-22-163B, X-22-163C, X-22-2000, X-22-4741, KF1005 and X-22-169B, X-22 Epoxy modified oleic oils such as -173DX; amine modified eucalyptus oils such as KF393, KF865, X-22-9409, X-22-3939A and X-22-161B; X-22-2445 and X-22- 1602 and other acrylic modified 矽 Oil; methacrylic acid modified eucalyptus oil such as X-22-164B and KF2012; carboxy modified eucalyptus oil such as X-22-3701E and X-22-X-22-162C; phenol modified eucalyptus oil such as KF2200; KF2001 and X-22-167B and other sulfhydryl modified eucalyptus oil; KF414 and KF4003 and other alkyl modified eucalyptus oil; KF410 and X-22-1877 and other aralkyl modified eucalyptus oil; X-22-176DX and X-22-176GX -A diol modified oleic oil; X-22-4272, KF945, KF6011, KF6123, X-22-2516, etc. polyether modified eucalyptus oil; X-21-5841 and KF9701 and other sterol based terminal eucalyptus oil.

The modified eucalyptus oil can be appropriately selected depending on the kind of the thermoplastic resin used in the adhesive composition. For example, when a hydrocarbon resin and an elastomer are used as the thermoplastic resin, it is preferred to introduce a methanol group, an epoxy group, an amine group, an acryl group, a methacryl group, a carboxyl group, a phenol group, a decyl group, or a decyl group. An eucalyptus oil modified with a highly polar functional group such as a diol or a polyether is used as a release agent.

The elastic system including hydrocarbon resin and hydrogenated styrene elastomer has a low polarity chemical structure. Therefore, when the modified eucalyptus oil having a functional group having a high polarity is blended, the modified eucalyptus oil can be more appropriately ooze out to the surface of the adhesive layer 3. Therefore, an adhesive capable of more appropriately adjusting the adhesion between the interface between the adhesive layer 3 of the laminate 10 shown in FIG. 1(a) and the substrate 1 and the interface between the adhesive layer 3 and the support sheet 2 can be obtained. Composition.

In other words, when the modified eucalyptus oil having a highly polar functional group is blended, the adhesiveness of the adhesive composition having high heat resistance such as an elastomer such as a hydrocarbon resin or a hydrogenated styrene elastomer can be appropriately adjusted.

Further, as the release agent, dimethyl hydrazine oil may also be used. And a modified eucalyptus oil having a low polarity functional group such as an alkyl group, a phenyl group or an aralkyl group. In other words, the fluorenone such as the dimethyl hydrazine oil and the modified eucalyptus oil may be appropriately selected and used depending on the polarity of the thermoplastic resin, the plasticizer, and the like used in the adhesive composition.

In the adhesive composition of one embodiment, the dynamic viscosity of the dimethyl hydrazine oil or the modified eucalyptus oil at 25 ° C is preferably 20 mm ² /s or more, more preferably 40 mm ² /s or more, and most preferably 60 mm ² /s. the above. If the kinetic viscosity of dimethyl hydrazine oil or modified eucalyptus oil at 25 ° C is 20 mm ² /s or more, the eucalyptus oil can be prevented from evaporating. Therefore, an adhesive composition of one embodiment can also be used for the laminate which is treated at a high temperature of, for example, 160 ° C or higher.

Further, the dimethyl hydrazine oil or the modified eucalyptus oil is not particularly limited as long as it is mixed in the thermoplastic resin, and it is preferable to use a dynamic viscosity at 25 ° C of 1,000,000 mm ² /s or less. When it is a dimethyl hydrazine oil or a modified eucalyptus oil having a dynamic viscosity of 1,000,000 mm ² /s or less at 25 ° C, it can be appropriately mixed with a thermoplastic resin, and the adhesion of the adhesive layer can be adjusted.

In addition, the blending amount of the dimethyl hydrazine oil or the modified eucalyptus oil with respect to the total amount of the thermoplastic resin may be appropriately adjusted depending on the type of the thermoplastic resin, the type of the thermoplastic resin, and the type of the releasing agent. Therefore, the release agent is preferably blended in a range of 0.01% by weight or more and 10% by weight or less, more preferably 0.1% by weight or more and 5% by weight or less, based on the total amount of the thermoplastic resin. The blending within the range is preferably in the range of 1% by weight or more and 3% by weight or less. When the dimethyl hydrazine oil or the modified eucalyptus oil is blended in a range of 0.01% by weight or more and 10% by weight or less based on the total amount of the thermoplastic resin, the substrate 1 and the support can be appropriately bonded. Hold the board 2. Further, an adhesive composition which can form a laminate in which the support sheet 2 can be easily peeled off from the substrate 1 even without forming a separation layer on the support sheet 2 can be obtained.

Further, a mold release agent such as dimethyl hydrazine oil or modified eucalyptus oil is preferably used in a proportion of a specific gravity close to a mixture of a thermoplastic resin and a solvent. Thereby, the dispersibility of the release agent to the adhesive composition can be improved.

(modified hardened oil of oyster sauce)

A hardened material of the modified eucalyptus oil can also be used as the release agent. The adhesion of the adhesive composition can also be appropriately adjusted by adding the cured product of the modified eucalyptus oil to the adhesive composition.

The cured product of the modified eucalyptus oil may be obtained by reacting a functional group introduced into the modified eucalyptus oil with a functional group of another modified eucalyptus oil. For example, an amine-modified eucalyptus oil or a thiol-modified eucalyptus oil may be reacted with an epoxy-modified eucalyptus oil.

Further, the cured product of the modified eucalyptus oil may be a cured product obtained by reacting, for example, a catalyst hardening type or a light hard type eucalyptus oil. Examples of the catalyst hardening type eucalyptus oils include KF-705F-PS, KS-705F-PS-1, and KS-770-PL-3 manufactured by Shin-Etsu Chemical Co., Ltd. Further, examples of the hard-type eucalyptus oil include KS-720 and KS744-PL3 manufactured by Shin-Etsu Chemical Co., Ltd.

Further, in the case of the cured product of the modified eucalyptus oil, a modified eucalyptus oil having a functional group having an active hydrogen introduced, such as a methanol modified eucalyptus oil or an amine modified eucalyptus oil, may be reacted with an isocyanate to obtain a cured product. Its work Used as a release agent.

[other ingredients]

The composition of the subsequent composition may further contain other substances having a miscibility, in addition to the thermoplastic resin and the release agent, within a range not impairing the essential properties. For example, various conventional additives such as an additive resin, a plasticizer, an auxiliary agent, a stabilizer, a colorant, a thermal polymerization inhibitor, and a surfactant for improving the performance of the adhesive can be further used. Further, the adhesive composition may also contain a diluent solvent.

(diluted solvent)

The dilution solvent is used to dilute the adhesive composition. Thereby, the adhesive composition can be adjusted to a viscosity suitable for the conditions for coating.

The diluent solvent may, for example, be a linear hydrocarbon such as hexane, heptane, octane, decane, methyl octane, decane, undecane, dodecane or tridecane; carbon number 4 to a branched hydrocarbon of 15, for example, a cyclic hydrocarbon such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene or tetrahydronaphthalene, p-menthane, o-menthane, metamenthane, diphenyl. Mentane, 1,4-decanediol, 1,8-nonanediol, borneol, norbornane, decane, oxane, decane, longene, geraniol, nerol, linalool , citral, citronellol, menthol, isomenthol, neomenthol, alpha-terpineol, beta-terpineol, gamma-terpineol, steroid-1-ol, steroid-4-ol , dihydrofurfuryl acetate, 1,4-decyl oleyl alcohol, 1,8-nonyl oleyl alcohol, borneol, carvone, ionone, flavonoids, camphor, d-limonene, l-limonene, dipentane Terpene solvent such as ene; γ- Lactones such as butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone; Polyols such as diethylene glycol, propylene glycol, dipropylene glycol, etc.; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, etc. a polyhydric alcohol such as a compound, a polyhydric alcohol or a monomethyl ether of a compound having an ester bond, a monoalkyl ether such as monoethyl ether, monopropyl ether or monobutyl ether, or a compound having an ether bond such as monophenyl ether. Derivatives (such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME)); cyclic ethers such as dioxane, or methyl lactate or ethyl lactate (EL) ), esters of methyl acetate, ethyl acetate, butyl acetate, butyl methoxyacetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, etc. An aromatic organic solvent such as anisole, ethylanisole, tolylmethyl ether, diphenyl ether, diphenyl ether, phenethyl ether or butylphenyl ether.

<Layer 10>

The laminate 10 according to an embodiment of the present invention will be described in more detail with reference to Fig. 1(a). As shown in Fig. 1, the laminate 10 is obtained by laminating the substrate 1 and the support sheet 2 of the support substrate 1 via the adhesive layer 3 formed using the adhesive composition of one embodiment of the present invention.

The substrate 1 of the laminate 10 is subjected to a desired treatment. As an example, the substrate 1 is thinned by a polishing machine or the like to have a thickness of 25 μm to 150 μm. Moreover, after the substrate 1 is thinned to a desired thickness, photolithography or the like is performed, and a circuit element or the like is formed on the substrate 1. That is, by applying force or heating to the laminate 10 of one embodiment, the adhesion of the adhesive layer 3 including the release agent can be adjusted, and the substrate 1 can be appropriately adhered to the support sheet 2.

Further, even if the laminate 10 is not provided with the separation layer, the support sheet 2 can be easily peeled off from the substrate 1 after the desired treatment. Therefore, it is not necessary to consider the chemical resistance and adhesion of the separation layer as in the case of the laminate having the separation layer, and the substrate 1 can be subjected to a desired treatment.

In addition, the separation layer is a layer provided between the support of the laminate and the adhesive layer, that is, an organic film such as a fluorocarbon film formed by a plasma CVD method or an inorganic film such as a metal film. Layer. The separation layer can be deteriorated by absorbing light to lower the strength or adhesion, thereby peeling off the support from the substrate.

[Substrate 1]

The substrate 1 is bonded to the support plate 2 via the adhesive layer 3 . As the substrate 1, the germanium wafer substrate is not limited, and any substrate such as a ceramic substrate, a thin film substrate, or a flexible substrate can be used.

[Support Board 2]

The support plate (support) 2 is a support for supporting the substrate 1 and is bonded to the substrate 1 via the adhesive layer 3 . Therefore, the support plate 2 may have strength required to prevent breakage or deformation of the substrate 1 when the substrate 1 is thinned, transported, or packaged. From the above viewpoints, examples of the support plate 2 include glass, enamel, and acrylic resin.

[Next layer 3]

This is a layer for bonding the substrate 1 and the support sheet 2, and is formed using the adhesive composition of one embodiment of the present invention. Next, the layer 3 is preferably formed by adjusting the appropriate viscosity of the adhesive composition by diluting the solvent according to the coating method of the adhesive composition and the film thickness of the adhesive layer 3.

Next, the layer 3 can be formed by applying the adhesive composition to the substrate 1 or the support sheet 2 by, for example, spin coating, dipping, roll knives, spray coating, slit coating, or the like.

The thickness of the layer 3 may be appropriately set depending on the type of the substrate 1 and the support sheet 2 to be bonded, the treatment to be performed on the bonded substrate 1 and the like. Here, the thickness of the subsequent layer 3 is preferably in the range of 10 μm or more and 150 μm or less, more preferably in the range of 15 μm or more and 100 μm or less.

<Peeling method of the first embodiment>

The peeling method of one embodiment (first embodiment) will be described in more detail with reference to Fig. 1 . The peeling method of the present embodiment includes a pretreatment step (Figs. 1(a) and (b)) for removing at least a part of the outer peripheral portion of the adhesive layer 3 of the laminate 10 according to the embodiment of the present invention, and a laminate. The substrate 1 of 10 peels off the peeling step of the support sheet 2 (Fig. 1 (c)).

Thereby, in the pre-treatment step, the force applied to the laminate 10 in the peeling step can be concentrated in the laminate 10 to remove the adhesive layer 3 part. Thereby, the support plate 2 can be peeled off from the substrate 1 without applying a great force to the laminate 10 in the peeling step.

Therefore, according to the peeling method of the present embodiment, it is not necessary to provide the separator 10 with a separation layer which is deteriorated by absorbing light.

Further, as shown in (d) and (e) of Fig. 1, in the peeling method of the present embodiment, after the peeling step, the peeling of the adhesive layer from the substrate 1 from which the support sheet 2 is peeled off is peeled off. step.

Thereby, the adhesive layer 3 can be appropriately removed from the substrate 1 from which the support sheet 2 is peeled off.

[pre-processing step]

The pretreatment step is performed by fixing the laminate 10 so that the substrate 1 of the laminate 10 is located on the bottom surface side (Fig. 1(a)). The fixing of the laminate is preferably carried out by a base (not shown) having a porous portion as an example.

As shown in FIG. 1(b), in the pre-processing step of the present embodiment, at least a part of the outer peripheral portion of the adhesive layer 3 of the laminate 10 is inserted into an insert member such as a doctor blade 20. Thereby, a part of the adhesive layer 3 following the support plate 2 is removed.

The doctor blade 20 is preferably inserted into the vicinity of the interface between the support plate 2 and the adhesive layer 3 of the laminate 10 shown in Fig. 1(b). Further, the depth to which the doctor blade 20 is inserted into the adhesive layer 3 is not limited, and is preferably at least 2 mm or more from the end portion of the outer peripheral portion of the adhesive layer 3, more preferably 2 mm or more and 10 mm or less.

Next, the stripping solvent S is supplied to the portion of the subsequent layer 3 which is removed by the doctor blade 20. Thereby, the adhesion of the portion of the laminate 10 from which a part of the subsequent layer 3 is removed can be reduced.

In the pre-treatment step, the amount of the stripping solvent S supplied to the portion of the laminate 10 through which the layer 3 is removed may be appropriately adjusted depending on the size of the laminate or the like, and is not limited, but may be at least 10 ml. The stripping solvent S may be supplied to the portion from which the adhesive layer 3 is removed, and it is more preferable that the stripping solvent S in an amount of 10 ml or more and 50 ml or less is supplied to the portion from which the adhesive layer 3 is removed. By supplying at least 10 ml of the stripping solvent S to the portion from which the subsequent layer 3 is removed, the adhesion of the adhesive layer 3 can be more appropriately lowered. Further, the supply of the peeling solvent S to the adhesive layer 3 can be carried out by a known means such as a spray nozzle, a dispensing nozzle, and a two-fluid nozzle.

In the pretreatment step, the release solvent S may be supplied to the adhesive layer 3 to such an extent that the adhesion of the portion from which the adhesive layer 3 is removed can be reduced. That is, the release solvent is supplied to the laminate until the support sheet can be peeled off from the substrate without dissolving the adhesive layer.

(stripping solvent)

The stripping solvent is a solvent supplied to the portion of the laminate 10 from which the layer 3 is removed in the pretreatment step to reduce the adhesion of the layer 3. The release solvent is not particularly limited as long as it is appropriately selected depending on the type of the thermoplastic resin and the release agent contained in the adhesive layer 3, and for example, the above-mentioned diluent solvent or the solvent listed below can be used.

Examples of the release solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; lactones such as γ-butyrolactone; acetone and methyl ethyl Ketones such as ketone (MEK), cyclohexanone (CH), methyl n-amyl ketone, methyl isoamyl ketone, 2-heptanone, etc.; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc. Polyols; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the aforementioned polyols or the aforementioned esters a derivative of a polyhydric alcohol such as a monomethyl ether of a compound of a bond, a monoalkyl ether such as monoethyl ether, monopropyl ether or monobutyl ether or a compound having an ether bond such as monophenyl ether (these are preferably Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME)); cyclic ethers such as dioxane, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, acetic acid An ester of butyl ester, butyl methoxyacetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, etc.; anisole, ethyl anisole, Tolyl methyl ether Diphenyl ether, anisole, phenetole, butyl phenyl ether and aromatic organic solvents and the like.

[Peeling step]

As shown in FIG. 1(c), in the peeling step, the laminate 10 is fixed such that the substrate 1 is positioned on the bottom surface side, and the support plate 2 located on the upper surface side of the laminate 10 is biased. The substrate 1 of the laminate 10 peels off the support plate 2.

Here, since the laminate 10 has removed a portion of the adhesive layer 3 which is followed by the support sheet 2 by the pre-treatment step, the laminate is The force applied by the support plate 2 of 10 is concentrated on the portion from which the adhesive layer 3 is removed. Further, the portion from which the subsequent layer 3 is removed in the pre-treatment step has been lowered by the stripping solvent. Therefore, the force applied to the support plate 2 of the laminate 10 can be more appropriately concentrated on the portion from which the adhesive layer 3 is removed. Further, in the pre-processing step, as long as the adhesive layer 3 is previously removed to a depth of at least 2 mm or more from the end portion of the outer peripheral portion of the adhesive layer 3, the portion of the peeling layer 3 may be more appropriately removed in the peeling step. The applied force is concentrated.

Further, the peeling method of the present embodiment is suitably carried out on the laminate 10 of one embodiment. Here, the adhesive layer 3 of the laminate 10 is formed of an adhesive composition containing a release agent, and then the adhesion of the layer 3 is adjusted. Therefore, the support plate 2 can be easily peeled off from the substrate 1 without applying a great force to the laminate 10.

Further, in the laminate 10, since the adhesive layer 3 contains a release agent, the support sheet 2 can be peeled off from the substrate 1 at the interface with the adhesive layer 3. Therefore, the cleaning of the support plate 2 can be omitted, or the amount of the solvent for cleaning the support plate 2 can be reduced.

(peeling device)

The peeling method of this embodiment can be performed by a general peeling apparatus. For example, the peeling device may have at least a base (not shown) for fixing the laminated body 10 and a separating plate (not shown) for biasing the laminated body 10. In the case of the base, as an example, the porous portion of the laminate 10 can be fixed by suction by a decompression means. also, As for the separation plate, as an example thereof, it is preferable to provide a plurality of jigs capable of gripping the support plate 2. In addition, the separator plate preferably has a floating joint.

In the peeling step, for example, the laminate 10 is preferably fixed to the base such that the substrate 1 is on the bottom surface side, and the chamfered portion of the outer peripheral end portion of the support plate 2 is gripped by a separating plate having a plurality of jigs, and then The separator is raised to apply force to the laminate 10.

Further, in the peeling step, it is preferable to form a laminated body from the separating plate via a floating joint which is movable to form a circular track parallel to the plane of the laminated body 10 and an arcuate path perpendicular to the plane of the laminated body 10. 10 force.

When the laminate 10 is biased from the separation plate via the floating joint, and the force is concentrated on the portion from which the subsequent layer 3 is removed, the floating joint is movable to tilt the separation plate, and accordingly, the support plate 2 is inclined. Thereby, excessive force is applied to the support plate 2 and a part of the substrate 1. Therefore, it is possible to prevent the support plate 2 and the substrate 1 from being damaged by excessive force, and it is possible to more appropriately peel the support plate 2 from the substrate 1.

Further, according to the peeling method of one embodiment of the present invention, it is not necessary to provide a separation layer forming apparatus in which a separation layer is formed in a laminate.

[Next layer peeling step]

As shown in FIGS. 1(d) and 1(e), in the peeling method of the embodiment, after the peeling step, the peeling step of peeling off the adhesive layer 3 remaining on the substrate 1 is included.

In the laminate 10, the subsequent layer 3 contains a release agent. Therefore, when the adhesive layer 3 is cooled to a temperature lower than the glass transition temperature of the thermoplastic resin, the adhesive layer 3 can be peeled off from the substrate 1 while maintaining the film shape (Fig. 1 (d)). That is, the adhesive layer 3 remaining on the substrate 1 can be removed without using a large amount of solvent to dissolve the adhesive layer 3 (Fig. 1(e)). Therefore, the cleaning of the substrate 1 or the amount of the solvent used for the cleaning of the substrate 1 can be omitted.

Thereafter, the residue of the adhesive layer 3 remaining on the surface of the substrate 1 is removed by washing, and the substrate 1 is subjected to a desired treatment. For example, after the support sheet 2 is separated, the substrate 1 can be cleaned, and the semiconductor wafer can be manufactured from the substrate 1 by dicing.

According to the peeling method of the present embodiment, in the pretreatment step, the support sheet 2 can be easily peeled off from the substrate 1 by using a peeling solvent to such an extent that the adhesion of the adhesive layer 3 of the laminate 10 can be lowered. Further, the adhesive layer 3 can be peeled off from the substrate 1 and the support sheet 2 in a film state. Therefore, according to the peeling method of the present embodiment, the amount of the solvent can be reduced as compared with the method of peeling the support sheet from the substrate by dissolving the adhesive layer by a solvent.

<Peeling method of the second embodiment>

The peeling method of the present invention is not limited to the above embodiment (first embodiment). For example, the peeling method of the embodiment (second embodiment) includes a step of irradiating light (laser) to at least a part of the outer peripheral portion of the adhesive layer 3 of the laminate 11 according to the embodiment of the present invention (Fig. 2 ( a) and (b)), and peeling off the support plate 2a from the substrate 1 of the laminate 11. The stripping step (Fig. 2(c)). That is, the peeling method of the present embodiment performs an illumination step instead of the previous processing step. Further, the peeling step (Fig. 2(c)) and the peeling step (Fig. 2(d) and (e)) performed after the illuminating step are the same as those of the first embodiment. Therefore, the description is omitted.

[illumination step]

As shown in Fig. 2(a), in the peeling method of the present embodiment, the laminate 11 is formed using a support plate 2a made of ruthenium. Since the laminate 11 is provided with the support plate 2a made of ruthenium, it is possible to appropriately penetrate infrared rays such as a carbon dioxide laser.

Further, the thermal expansion coefficient of the support plate 2a made of ruthenium and the substrate 1 can be made slightly equal. Therefore, even if the laminate 11 is treated at a high temperature by, for example, a CVD process or the like, the distortion of the substrate 1 due to the difference in thermal expansion coefficient between the support plate 2a and the substrate 1 can be appropriately prevented.

Further, even when glass is used as the support plate, infrared rays such as carbon dioxide laser can be appropriately penetrated from the substrate 1 side. In other words, by irradiating the infrared rays from the substrate 1 side, a support plate made of glass can be used as the support plate 2a instead of the support plate made of tantalum.

Further, since the subsequent layer 3 contains an anthrone as a releasing agent, the structure of the fluorenone of the fluorenone can be absorbed.

As shown in FIG. 2(b), in the illuminating step, at least a part of the outer peripheral portion of the subsequent layer 3 is irradiated with light L from the side of the support plate 2a of the laminate 11 using the carbon dioxide laser irradiation device 21. With this, you can The adhesive layer 3 of the outer peripheral portion of the laminate 11 illuminates light (infrared rays) that can penetrate the support plate 2a. Thereby, the adhesive layer 11 absorbs infrared rays in the adhesive layer 3, and by this energy, the adhesive layer 3 containing an anthrone is deformed, whereby the adhesive force of the support plate 2a and the adhesive layer 3 can be reduced.

In addition, in the present specification, the term "deterioration" of the adhesive layer containing anthrone refers to a phenomenon in which the adhesive layer containing an anthrone is subjected to only a slight external force (for example, about 0.1 to 5 Kgf), which may be destroyed. The state, or a state in which the adhesion of the layer in contact with the adhesive layer containing the fluorenone is lowered. As a result of deterioration of the adhesive layer containing anthrone due to absorption of light, the adhesive layer containing anthrone has lost strength or adhesion before irradiation with light. That is, the adhesive layer containing an anthrone is embrittled by light absorption. The "deformation of the adhesive layer containing an anthrone" may be a decomposition caused by energy of light absorbing the substance constituting the adhesive layer containing an anthrone, a change in a stereoscopic arrangement, or a dissociation of a functional group. The metamorphism of the adhesive layer comprising an anthrone is caused by the absorption of light by the anthrone. Therefore, the substrate and the support plate can be biased by irradiating light to the peripheral end portion of the laminate containing the fluorenone in the laminate to concentrate the force on the peripheral end portion of the subsequent layer embrittlement. Thereby, the substrate and the support plate can be appropriately separated.

Further, in the illuminating step, the laminated body 11 is fixed in the same manner as the above-described previous processing steps, and the fixing method and the fixing means may be the same as the above-described previous processing steps.

(lighting of light)

The laser beam which emits light irradiated to at least a part of the adhesive layer 3 is typically infrared (0.78 μm or more and 1000 μm or less), preferably far infrared ray (3 μm or more and 1000 μm or less), more preferably 9 μm. Above and below 11 μm light. Specifically, it is a CO ₂ laser. By using a CO ₂ laser, the subsequent layer 3 can be made to absorb the aforementioned CO ₂ laser. This is because the adhesive layer (for example, eucalyptus oil) is contained in the adhesive layer 3, and the above-mentioned release agent has a Si—O bond, so that infrared rays such as a CO ₂ laser can be absorbed. Therefore, the adhesion layer 3 containing an anthrone can be deteriorated by irradiation of infrared rays such as a CO ₂ laser, and the adhesion layer 3 can be made embrittled.

The average output power value of the laser is preferably 1.0 W or more and 50.0 W or less, more preferably 3.0 W or more and 40.0 W or less in terms of the irradiation conditions of the laser in the illumination step. The repetition frequency of the laser is preferably 20 kHz or more and 60 kHz or less, more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser is preferably 100 mm/s or more and 10,000 mm/s or less, more preferably 100 mm/s or more and 1000 mm/s or less. Thereby, the irradiation condition of the laser can be set to an appropriate condition for deteriorating at least a part of the adhesive layer 3. Further, the beam spot diameter of the continuous light and the irradiation pitch of the continuous light may be such that the adjacent beam spots do not overlap and the at least a portion of the layer 3 can be deteriorated.

Further, in the illuminating step included in the peeling method of the present embodiment, it is preferable that the edge of the peripheral portion of the support plate 2a is directed inward, and the subsequent layer 3 in the range of 10 mm or less is irradiated with light, more preferably The subsequent bonding layer 3 in the range of 5 mm or less is irradiated with light, and the light-based layer 3 is preferably irradiated to the subsequent bonding layer 3 in the range of 2 mm or less. Thereby, when the substrate 1 and the support plate 2a are separated, the force can be concentrated on the outer periphery of the laminate 11. The outer peripheral portion of the layer 3 is lowered by the force. Further, by this, it is possible to prevent the light that penetrates the support plate 2a and the adhesive layer 3 from damaging the components formed on the inner side of the substrate 1. Further, in the case of the illuminating step, it is also possible to illuminate the adhesive layer 3 from the side of the substrate 1 to the inside.

<Peeling method of another embodiment>

The peeling method of the embodiment of the present invention is not limited to the above embodiment. For example, in the illuminating step included in the peeling method of the second embodiment, the laminated body 10 is used, and the outer layer of the laminated body 10 is irradiated with light to the adhesive layer 3 in the illuminating step.

According to the above configuration, since the adhesive layer 3 contains an anthrone as a release agent, it is not necessary to allow the light to penetrate the substrate 1 or the support sheet 2 of the laminate 10, and the outer peripheral portion of the adhesive layer 3 is irradiated with light, so that the adhesive layer 3 can be absorbed. Light. Thereby, the adhesion of the support plate 2 and the adhesive layer 3 can be reduced. Further, the substrate 1 can also be peeled off from the laminate 10 in the same manner.

The peeling method of the present invention is not limited to the above embodiment. For example, in the peeling method of the embodiment, in the pretreatment step, an embodiment in which the supply of the peeling solvent is not performed on the outer peripheral portion of the adhesive layer of the laminate may be employed. The supply of the stripping solvent may be determined depending on the adhesion of the adhesive composition of one embodiment for forming the laminate.

When the support sheet 2 is to be peeled off from the substrate 1, the adhesion of the adhesive layer 3 is adjusted so that a peel strength of less than 1.5 kgf can be achieved, and in the pretreatment step, the supply of the peeling liquid can be omitted.

Further, in another embodiment, the peeling method may be in a form not including the adhesive layer peeling step. The substrate 1 may be removed from the support layer 2 by the cleaning liquid, and the subsequent layer 3 may be removed by a cleaning liquid, depending on the type of the substrate and the composition of the adhesive.

Furthermore, in still another embodiment, the support plate 2 may be fixed to a base or the like, and the substrate 1 may be biased. Thereby, the support plate 2 can be easily peeled off from the substrate 1.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims. The embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the technical scope of the present invention.

[Examples] [Preparation of the composition of the adhesive]

First, as Examples 1 to 35, an adhesive composition having different types of adhesives, types of release agents, and blending amounts was prepared. Further, as Comparative Examples 1 to 5, an adhesive composition containing no release agent was prepared.

The resin used as the thermoplastic resin of the adhesive composition is Taftec (trade name) H1051 (SEBS; hydrogenated styrene-based thermoplastic elastomer; styrene content 42%, Mw = 78,000) manufactured by Asahi Kasei Co., Ltd., and limited KURARAY shares. Septon 2002 (SEPS: styrene-isoprene-styrene block) and Septon 8004 (SEP: polystyrene-poly(ethylene/propylene) manufactured by the company Septon (trade name) Block), Septon V9827 (reactive crosslinked styrene-ethylene-butylene-styrene block copolymer), TOPAS (trade name) TM (polyolefin copolymer; ethylene-norbornene) manufactured by Polyplastics Co., Ltd. Copolymer, Mw = 10,000, Mw / Mn = 2.08, norbornene: ethylene = 50:50 (by weight), APL8008T manufactured by Mitsui Chemicals Co., Ltd. (cycloolefin copolymer, ethylene: tetracyclododecene = 80:20) Copolymer) and acrylic copolymer A1 (styrene / dicyclopentenyl methacrylate / octadecyl methacrylate = 20/60 / 20 (by weight) copolymer, molecular weight 10000).

Further, as a thermal polymerization inhibitor (additive), "IRGANOX (trade name) 1010" manufactured by BASF Corporation was used. Further, as the main solvent, decalin was used. Further, as an additive solvent, butyl acetate was used.

[Manufacturing Example 1]

First, a thermoplastic resin in which H1051, Septon 2002, and TOPASTM were mixed in a weight ratio of 55:45:10 was dissolved in a solvent having a weight ratio of decalin:butyl acetate of 15:1 to a concentration of 28% by weight. Next, IRGANOX 1010 was added so that the amount of the solid content of the thermoplastic resin was 1% by weight to obtain the adhesive composition A.

Next, the release agent was blended with the adhesive composition A according to the type and blending amount of the release agent shown in Table 1, and the adhesive compositions of Examples 1 to 11 were prepared. Further, the blending amount of the releasing agent shown in Table 1 is represented by the weight ratio of the solid resin component in the adhesive composition A. Further, an adhesive composition A containing no release agent was prepared as Comparative Example 1.

Table 2 below shows details of the physical property values of the release agents used in Examples 1 to 11. In addition, the release agents of KF6003 to KF6123 in Table 2 are all manufactured by Shin-Etsu Chemical Co., Ltd.

[Manufacturing Example 2]

First, a thermoplastic resin in which Septon V9827, Septon S2002, TOPASTM, and acrylic copolymer A1 are mixed in a weight ratio of 50:20:15:15 is dissolved in decalin: butyl acetate in a weight ratio of 15:1. In the solvent, the concentration was made 28% by weight. Next, IRGANOX 1010 was added so that the amount of the solid content of the thermoplastic resin was 1% by weight to obtain the adhesive composition B.

Next, the release agent was blended with the adhesive composition B according to the type and blending amount of the release agent shown in Table 3 to prepare the adhesive compositions of Examples 12 to 17. Further, the blending amount of the releasing agent shown in Table 3 is represented by the weight ratio of the solid resin component in the adhesive composition B. Further, an adhesive composition B containing no release agent was prepared as Comparative Example 2.

The details of the physical property values of the release agents used in Examples 12 to 17 are the same as those described in Table 2 above.

[Manufacturing Example 3]

First, a thermoplastic resin in which Taftec H1051, Septon S2002, TOPASTM, and acrylic copolymer A1 are mixed in a weight ratio of 52:26:11:11 is dissolved in a solvent having a weight ratio of decahydronaphthalene:butyl acetate of 15:1. The concentration was made 28% by weight. Next, IRGANOX 1010 was added so that the amount of the solid content of the thermoplastic resin was 1% by weight to obtain the adhesive composition C.

Next, the release agent was blended on the adhesive composition C according to the type and blending amount of the release agent shown in Table 4 to prepare the adhesive compositions of Examples 18 to 23. Further, the blending amount of the releasing agent shown in Table 4 is represented by the weight ratio of the solid content of the resin in the adhesive composition C. Further, an adhesive composition C containing no release agent was prepared as Comparative Example 3.

The details of the physical property values of the release agents used in Examples 18 to 23 are also the same as those described in Table 2 above.

[Manufacturing Example 4]

Septon 8004, which is a thermoplastic resin, was dissolved in a solvent having a weight ratio of decalin:butyl acetate of 15:1 to a concentration of 28% by weight. Next, IRGANOX 1010 was added so that the amount of the solid content of the thermoplastic resin was 1% by weight to obtain the adhesive composition D.

Next, the release agent was blended with the release agent D according to the type and blending amount of the release agent shown in Table 5, and the adhesive compositions of Examples 24 to 29 were prepared. Further, the blending amount of the releasing agent shown in Table 5 is represented by the weight ratio of the solid resin component in the adhesive composition D. Further, an adhesive composition D containing no release agent was prepared as Comparative Example 4.

The details of the physical property values of the release agents used in Examples 24 to 29 are also the same as those described in Table 2 above.

[Manufacturing Example 5]

APL8008T as a thermoplastic resin was dissolved in a solvent having a weight ratio of decalin:butyl acetate of 15:1 to a concentration of 28% by weight. Next, IRGANOX 1010 was added so that the amount of the solid content of the thermoplastic resin was 1% by weight to obtain an adhesive composition E.

Next, the release agent was blended with the adhesive composition E according to the type and blending amount of the release agent shown in Table 6, and the adhesive compositions of Examples 30 to 35 were prepared. Further, the blending amount of the releasing agent shown in Table 6 is represented by the weight ratio of the solid resin component in the adhesive composition E. Further, an adhesive composition E containing no release agent was prepared as Comparative Example 5.

The details of the physical property values of the release agents used in Examples 30 to 35 are also the same as those described in Table 2 above.

Next, using the adhesive compositions of Examples 1 to 35 and Comparative Examples 1 to 5, the applicability of the adhesive composition and the support were evaluated in each step of applying the adhesive composition to the release of the support. Adhesion, adhesion and peelability.

(Evaluation of the applicability of the adhesive composition)

After the adhesive compositions of Examples 1 to 35 and Comparative Examples 1 to 5 were applied onto a substrate to form an adhesive layer, the applicator composition was evaluated for applicability.

First, the semiconductor wafer substrate (12 Å; 矽) was spin-coated with the adhesive composition of Example 1, and baked at a temperature of 90 ° C, 160 ° C, and 220 ° C for 4 minutes to form an adhesive layer (film thickness). 50 μm). Thereafter, the semiconductor wafer substrate on which the adhesive layer was formed was rotated at 1,500 rpm while being supplied by an EBR nozzle at a supply amount of 10 cc/min. TZNR (registered trademark) HC Thinner (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 5 to 15 minutes, whereby the outer peripheral portion of the adhesive layer formed on the outer peripheral portion of the semiconductor wafer substrate is the end of the semiconductor wafer substrate The portion was removed to the inside from the bottom layer to 1.3 mm. Further, the bonding layers of Examples 2 to 35 and Comparative Examples 1 to 5 were formed on the substrate in accordance with the same procedure.

Thereafter, the coating properties of Examples 1 to 35 and Comparative Examples 1 to 5 were evaluated. The coatability is evaluated based on whether or not white smoke is generated at the time of coating according to the adhesive layer formed on the semiconductor wafer substrate. The coating property was visually evaluated, and when the adhesive composition was applied to the semiconductor wafer substrate and baked at 90 ° C, 160 ° C, and 220 ° C for 4 minutes, it was not formed on the semiconductor wafer substrate. Then, those who emit white smoke are rated as "○", and those who emit white smoke are rated as "X". Further, when the heat resistance of the release agent is insufficient, it is decomposed during baking and observed as white smoke.

(Evaluation of the fabrication and fit of the laminate)

Next, a semiconductor wafer substrate in which an adhesive layer was formed using the adhesive compositions of Examples 1 to 35 and Comparative Examples 1 to 5 was used to fabricate a laminate. Thereafter, the evaluation of the fit of each laminate was carried out.

First, the semiconductor wafer substrate, the subsequent layer, and the support were sequentially superposed on the semiconductor wafer substrate coated with the adhesive composition of Example 1, and under vacuum (5 Pa) and 215 ° C, 4,000. The bonding pressure of kgf was pressed for 2 minutes to bond the support to the semiconductor wafer substrate. In addition, the above support system uses glass with a size of 12 inches. Support body. Further, the laminates of Examples 2 to 35 and Comparative Examples 1 to 5 were produced in the same manner.

Thereafter, the laminates of Examples 1 to 35 and Comparative Examples 1 to 5 were evaluated for adhesion. The fit was evaluated by visual observation, and the laminate having no voids and the like was evaluated as "○", and the laminate having no subsequent portion was evaluated as "X".

(Evaluation of adhesion after back grinding treatment)

Then, the back surface of the semiconductor wafer substrate of the laminates of Examples 1 to 35 and Comparative Examples 1 to 5 was thinned by a back surface polishing apparatus manufactured by DISCO Corporation until the thickness of the semiconductor wafer substrate was 50 μm (back grinding treatment: BG treatment) ). Thereafter, the adhesion of the support after the BG treatment was evaluated for each laminate. The adhesion was evaluated by visual observation, and the laminate in which the support was not peeled off was evaluated as "○", and the laminate in which peeling was observed was evaluated as "X".

(Assessment of heat resistance by CVD treatment)

Next, the laminates of Examples 1 to 35 and Comparative Examples 1 to 5 subjected to the BG treatment were subjected to plasma CVD treatment using N ₂ at 220 ° C for 10 minutes. Thereafter, the heat resistance was evaluated for each laminate. The heat resistance was evaluated by visual evaluation, and the exposed portion of the edge portion without the laminate or the void between the laminates was evaluated as "○", and the laminate having the exposed or unattached portion was evaluated as "X".

(evaluation of peelability)

Next, the laminates of Examples 1 to 35 and Comparative Examples 1 to 5 subjected to the plasma CVD treatment were subjected to a pretreatment step and a peeling step to evaluate the peelability.

First, the doctor blade was inserted to a depth of 2 mm from the end portion of the outer peripheral portion of the laminate of Example 1, and thereafter, a pretreatment step was carried out by supplying 10 ml of ethanol as a stripping solvent to the portion where the blade was inserted into the laminate. Then, a TWR 12000 series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used as a support separation device, and the semiconductor wafer substrate side was fixed, and a support step was applied to the support side. The peelability was evaluated by rating the laminate from which the glass support was peeled off from the semiconductor wafer substrate to "○" and the laminate which could not be peeled off as "X". Further, the laminates of Examples 2 to 35 and Comparative Examples 1 to 5 were evaluated for peelability in accordance with the same procedure.

(Evaluation Results)

The results of evaluation of coating properties, adhesion, adhesion, heat resistance and peelability of Examples 1 to 35 and Comparative Examples 1 to 5 are shown in Tables 7 to 11 below:

As shown in Tables 7 to 11, when the adhesive compositions of Examples 1 to 35 were used, it was confirmed that coating properties comparable to those of the adhesive compositions of Comparative Examples 1 to 5 containing no release agent were obtained. Properties, adhesion and heat resistance. Further, by performing the pretreatment step, it was confirmed that the glass support can be appropriately peeled off from the semiconductor wafer substrate.

In addition, as a result of the use of the composition of the adhesives of Examples 24 to 35, it was confirmed that the pre-treatment step was carried out by using a release agent containing a single component of the elastomer resin or the cycloolefin resin as a thermoplastic resin. Thereby, a laminate which can appropriately separate the support from the substrate can be formed.

[Evaluation of peel strength]

The laminates using the adhesive compositions of Examples 1 and 2 and Comparative Example 1 were evaluated for peel strength. Further, the evaluation of the peel strength was carried out under the same conditions as the evaluation of the peelability. Evaluation of peel strength The results are shown in Table 12.

As shown in Table 12, in the laminates of Examples 1 and 2, the peel strength when the support was peeled off from the semiconductor wafer substrate was less than 1.5 kgf. On the other hand, in the laminate of Comparative Example 1, the peel strength showed a value of 3.8 kgf or more, and the support could not be peeled off from the substrate without damaging the substrate and the support.

As a result of the evaluation, it was confirmed that the use of the adhesive composition according to the embodiment of the present invention can be suitably separated from the substrate by blending the release agent without vertically providing a separation layer which is deteriorated by absorption of light. The laminate of the support.

[Assessment of laminates using ruthenium support]

Using the adhesive compositions of Examples 1 to 35 and Comparative Examples 1 to 5, a laminate obtained by laminating a 12-inch ruthenium carrier (ruthenium support) and a semiconductor wafer substrate was prepared, and each of the adhesives was used. Evaluation of applicability, adhesion, adhesion, heat resistance, and peelability of the adhesive composition in the laminate of the material. Further, each laminate was produced under the same production conditions as those of the laminate using the glass support except that the ruthenium carrier was used. Again, for The evaluation conditions of the coatability, the adhesion, the adhesion, and the heat resistance of each laminate were also the same as those of the laminate using the glass support.

When the laminate compositions of Examples 1 to 35 and Comparative Examples 1 to 5 are used, and a laminate made of a 12-inch tantalum carrier (ruthenium support) and a semiconductor wafer substrate is used, glass support is also used. In the case of the laminate produced by the body, the evaluation of applicability, adhesion, adhesion, and heat resistance was "○".

[Assessment of peelability by light irradiation]

Using the laminates of Examples 1 to 35 and Comparative Examples 1 to 5, a laminate obtained by laminating a ruthenium carrier and a semiconductor wafer substrate was used as an object, and an illuminating step was carried out instead of the above-described previous treatment step to carry out releasability. Assessment.

Specifically, in the illuminating step, the CO ₂ laser is irradiated from the outer peripheral portion of each laminate to the inner side by a width of 5 mm from the side of the carrier, and then the semiconductor wafer substrate side is fixed, and 0.5 kgf is applied to the crucible carrier. Force to perform the stripping step.

The above-mentioned CO ₂ laser irradiation conditions are as follows: the average power of the laser: 100%, 20 W

Laser scanning speed: 500mm/sec.

The peelability was evaluated by applying a force of 0.5 kgf, and the person who can be peeled off from the semiconductor wafer substrate was rated as "○", and the person who could not be peeled off was rated as "x".

As a result of the evaluation of the peelability, for the use example The laminate of the adhesive composition of 1 to 35 can easily peel off the support (○) from the semiconductor wafer substrate. However, the laminates of Comparative Examples 1 to 5 produced using the adhesive composition-free adhesive composition were used to fix the semiconductor wafer substrate side after the illuminating step, and a force of 0.5 kgf was applied to the ruthenium carrier. It is still impossible to peel off the tantalum carrier (x) from the semiconductor wafer substrate.

(Assessment from the side of the substrate)

A laminate in which a semiconductor wafer substrate and a glass support of 12 Å were laminated using the adhesive compositions of Examples 1 to 35 and Comparative Examples 1 to 5 was produced. Further, in each of the laminates, the adhesive composition was applied under the conditions of the evaluation of the applicability, and the semiconductor wafer substrate and the glass support were bonded together under the conditions of the evaluation of the adhesion. Further, each of the laminates produced under the conditions was subjected to a BG treatment and a plasma CVD treatment, and thereafter, a CO ₂ laser was irradiated from the semiconductor wafer substrate side to a width of 5 mm from the outer peripheral portion of each laminate. The semiconductor wafer substrate side was fixed, and a force of 0.5 kgf was applied to the glass support to perform a peeling step. Further, the irradiation conditions of the CO ₂ laser in the illuminating step are the same as those of the embodiment in which the ruthenium carrier side illuminates.

As a result of the evaluation of the peeling property, the laminate using the adhesive compositions of Examples 1 to 35 can be easily peeled off from the semiconductor wafer substrate in the same manner as the evaluation result of the peeling property of the laminate using the ruthenium carrier. Support (○). Further, in the laminates of Comparative Examples 1 to 5, even after the illuminating step, the semiconductor wafer substrate side was fixed, and a force of 0.5 kgf was applied to the glass support, and the semiconductor wafer substrate could not be peeled off. Glass support (×).

As a result, it was confirmed that by using the adhesive composition of the present invention and by performing illumination instead of the above-described previous treatment step, the adhesive strength can be lowered, and a laminate which can appropriately peel the support from the substrate can be formed.

[Industrial Applicability]

The present invention can be widely utilized in, for example, a manufacturing step of a miniaturized semiconductor device.

1‧‧‧Substrate

2‧‧‧Support board (support)

3‧‧‧Next layer

10‧‧‧Layer

20‧‧‧Scraper

S‧‧‧ stripping solvent

Claims (10)

An adhesive composition for temporarily bonding a substrate and an adhesive composition supporting the support of the substrate, comprising a thermoplastic resin and a release agent. The adhesive composition according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of a hydrocarbon resin and an elastomer. The adhesive composition of claim 2, wherein the elastomer is a hydrogenated styrene elastomer. The adhesive composition according to any one of claims 1 to 3, wherein the release agent is derived from dimethyl fluorenone, and a functional group is introduced by at least a part of a terminal and a side chain of dimethyl fluorenone. At least one selected from the group of modified oxime ketones. The adhesive composition of claim 4, wherein the functional group is a methanol group, an epoxy group, an amine group, an acryl group, a methacryl group, a carboxyl group, a phenol group, a decyl group, an alkyl group, an aralkyl group, At least one functional group selected from the group consisting of sterol groups, diols, and polyethers. The adhesive composition of claim 4, wherein the dimethyl ketone or the above modified fluorenone has a dynamic viscosity at 25 ° C of 20 mm ² /s or more. The adhesive composition according to claim 4, wherein the release agent is blended in a range of 0.01% by weight or more and 10% by weight or less based on the total amount of the thermoplastic resin. A laminate comprising a substrate, and a support supporting the substrate, via an adhesive layer formed using the adhesive composition of claim 4 Fitted together. A peeling method comprising: a pre-treating step of removing at least a portion of an outer peripheral portion of the adhesive layer of the laminate of claim 8; and, after the pre-treating step, peeling off the support from the substrate of the laminate The stripping step of the body. A peeling method comprising: a step of illuminating at least a portion of an outer peripheral portion of the adhesive layer of the laminate of claim 8; and, after the illuminating step, peeling the support from the substrate of the laminate The stripping step.